metal-organic compounds
Acta Crystallographica Section E
Experimental
Structure Reports
Online
Crystal data
ISSN 1600-5368
Diaquadichloridobis(pyridine-jN)cobalt(II)
P.S. Kannan,a A. S. Ganeshraja,b K. Anbalagan,b
E. Govindanc and A. SubbiahPandic*
a
Department of Physics, S. R. R. Engineering College (A. Jeppiaar Institution), Old
Mamallapuram Road, Padur, Chennai 603 103, India, bDepartment of Chemistry,
Pondicherry University, Pondicherry 605 014, India, and cDepartment of Physics,
Presidency College (Autonomous), Chennai 600 005, India
Correspondence e-mail: [email protected]
[CoCl2(C5H5N)2(H2O)2]
Mr = 324.06
Triclinic, P1
a = 6.2028 (2) Å
b = 6.5971 (1) Å
c = 8.5963 (2) Å
= 109.734 (2)
= 102.621 (3)
= 97.031 (2)
V = 315.65 (1) Å3
Z=1
Mo K radiation
= 1.77 mm1
T = 293 K
0.25 0.2 0.18 mm
Data collection
Oxford Diffraction Xcalibur
diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2009)
Tmin = 0.576, Tmax = 0.618
2211 measured reflections
2211 independent reflections
1926 reflections with I > 2(I)
Refinement
Received 25 April 2013; accepted 10 August 2013
Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.006 Å;
R factor = 0.047; wR factor = 0.149; data-to-parameter ratio = 25.1.
The title molecule, [CoCl2(C5H5N)2(H2O)2], has 1 symmetry
with the CoII ion situated on an inversion centre. The cation
has a distorted octahedral coordination environment and is
surrounded by two N and two Cl atoms in the equatorial
plane, while the coordinating water O atoms occupy the axial
positions. The crystal exhibits nonmerohedral twinning with
two domain states, the volume fractions of which were refined
to 0.883 (2) and 0.117 (3). The crystal packing is stabilized by
O—H Cl hydrogen-bond interactions, forming two-dimensional networks lying parallel to (001). The crystal packing
also features – interactions between the pyridine rings, with
centroid–centroid separations of 3.493 (3) and 3.545 (3) Å.
Related literature
For biological activity and potential applications of mixedligand cobalt complexes, see: Arslan et al. (2009) (antimicrobial activity); Delehanty et al. (2008) (antiviral activity);
Sayed et al. (1992) (antitumor activity); Teicher et al. (1990)
(antitumor and cytotoxic activities); Milaeva et al. (2013)
(biochemical properties of CoII). For related structures, see: Li
et al. (2009); Zhu & Zhou (2008). For graph-set motifs, see:
Etter et al. (1990).
R[F 2 > 2(F 2)] = 0.047
wR(F 2) = 0.149
S = 1.16
2211 reflections
88 parameters
3 restraints
H atoms treated by a mixture of
independent and constrained
refinement
max = 0.71 e Å3
min = 0.99 e Å3
Table 1
Hydrogen-bond geometry (Å, ).
D—H A
i
O1—H1A Cl1
O1—H1B Cl1ii
D—H
H A
D A
D—H A
0.82 (3)
0.81 (4)
2.45 (3)
2.41 (4)
3.266 (3)
3.156 (3)
176 (5)
153 (4)
Symmetry codes: (i) x; y þ 1; z; (ii) x þ 1; y; z.
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell
refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97
(Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows
(Farrugia, 2012); software used to prepare material for publication:
SHELXL97 and PLATON (Spek, 2009) and TwinRotMat (Bolte,
2004).
ASP and PSK are thankful to the Department of Chemistry,
Pondicherry University, for the single-crystal XRD facility.
KA is thankful to CSIR, New Delhi (Lr: No. 01 (2570)/12/
EMR-II/3.4.2012), for financial support of a major research
project.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: FB2288).
References
Arslan, H., Duran, N., Borekci, G., Ozer, C. K. & Akbay, C. (2009). Molecules,
14, 519–527.
Bolte, M. (2004). J. Appl. Cryst. 37, 162–165.
Delehanty, J. B., Bongard, J. E., Thach, C. D., Knight, D. A., Hickeya, T. E. &
Chang, E. L. (2008). Bioorg. Med. Chem. 16, 830–837.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Li, N., Zou, H.-L., Song, X.-Y., Liu, Y.-C. & Chen, Z.-F. (2009). Acta Cryst.
E65, m1666.
m508
Kannan et al.
doi:10.1107/S1600536813022484
Acta Cryst. (2013). E69, m508–m509
metal-organic compounds
Milaeva, E. R., Shpakovsky, D. B., Gracheva, Y. A., Orlova, S. I., Maduar, V.
V., Tarasevich, B. N., Meleshonkova, N. N., Dubova, L. G. & Shevtsova, E. F.
(2013). Dalton Trans. 42, 6817–6828.
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO.
Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.
Sayed, G. H., Radwan, A., Mohamed, S. M., Shiba, S. A. & Kalil, M. (1992).
Chin. J. Chem. 10, 475–480.
Acta Cryst. (2013). E69, m508–m509
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Teicher, B. A., Abrams, M. J., Rosbe, K. W. & Herman, T. S. (1990). Cancer
Res. 50, 6971–6975.
Zhu, W.-F. & Zhou, X.-F. (2008). Acta Cryst. E64, m1478.
Kannan et al.
[CoCl2(C5H5N)2(H2O)2]
m509
supporting information
supporting information
Acta Cryst. (2013). E69, m508–m509
[doi:10.1107/S1600536813022484]
Diaquadichloridobis(pyridine-κN)cobalt(II)
P.S. Kannan, A. S. Ganeshraja, K. Anbalagan, E. Govindan and A. SubbiahPandi
S1. Comment
Mixed ligand cobalt complexes have found potential applications in the field of medicine because of its antitumor activity
(Teicher et al., 1990; Sayed et al., 1992), antiviral activity (Delehanty et al., 2008), antimicrobial activity (Arslan et al.,
2009) and radiosensitization and cytotoxic activities (Teicher et al., 1990).
Cobalt is essential and integral component of vitamin B12, therefore it is found in many tissues. Cobalt complexes are
useful in nutritional supplementation.
Electron transfer as well as ligand substitution reactions of cobalt(II) complexes are useful in understanding of
biochemistry of cobalt(II) (Milaeva et al., 2013). In order to study the electron transfer phenomena, the structure
determination of the title compound, C10H14Cl2Co1N2O2, has been carried out.
The title molecule is shown in Fig. 1. It possesses symmetry 1 because its central atom Co(II) is situated at the
crystallographic inversion centre. The Co(II) ion has a distorted octahedral coordination environment. It is surrounded by
two N atoms and two Cl atoms in the equatorial plane, while the water oxygens occupy the axial positions.
The bond lengths are comparable with those observed in the related structure of tetraaquabis(pyridine-kN)cobalt(II) bis[4-amino-N- (6-chloropyridazin-3-yl)-benzenesulfonamidate] (Li et al., 2009); tetraaquabis[5-(4-pyridyl)tetrazolidokN5]cobalt(II) dihydrate (Zhu & Zhou, 2008). The crystal packing is stabilized by O1-H1A···Cl1 and O1-H1B···Cl1
hydrogen bonds with the graph-set motif R24(8) (Etter et al., 1990) with H1a and H1b and its equivalents generated by
(iii): 1-x, 1-y, -z, and by two graph-set motifs R22(8) with the atoms H1a and H1ai or H1b and H1biv involved where (i): -x,
1-y, -z and (iv): 1-x, -y, -z (Table 1, Fig. 2).
There are also two π-electron ring···π-electron ring interactions between the pyridine rings N1//C1-C5 and the symmetry
equivalents related by the operations (v): -x, -y, 1-z and (vi): -x, 1-y, 1-z. The respective distances between the centroids
are 3.493 (3) and 3.545 (3)Å.
S2. Experimental
Diaquadichloridobis(pyridine-N)Cobalt(II) complex was prepared by dissolving cobalt(II) chloride hexahydrate
(CoCl2.6H2O, 1 g, 0.28 M) in boiling ethanol (C2H5OH, 15 ml). An excess of pyridine (C5H5N, 2.5 ml, 10 M) dissolved in
ethanol (2.0 ml), was added slowly to this mixture in order to precipitate the title complex. The crude pink coloured
precipitate was washed with cold ethanol and then air-dried. Then this precipitate was dissolved in 10-15 ml of hot
ethanol, cooled down and allowed to crystallize. After cooling pink coloured crystals (0.84 g) developed within 12 hours.
X-ray quality crystals were obtained by repeated recrystallization from hot ethanol. The typical size of the obtained
block-like crystals was 0.8 × 0.6 × 0.5 mm. (The measured sample has been cut from a larger crystal.)
Acta Cryst. (2013). E69, m508–m509
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supporting information
S3. Refinement
After the solution of the phase problem by SHELXS-97 (Sheldrick, 2008), the refinement on HKLF4 (SHELXL-97,
Sheldrick, 2008) converged to the R-factor equal to 0.067 for Fo>4σ(Fo). The difference electron density map showed
several peaks of the order of magintude of 1eÅ-3. A check by TwinRotMat (Bolte, 2004; PLATON (Spek, 2009)) showed
that the crystal had a two-fold non-merohedral twinning with the twin matrix [h2 k2 l2] = [h1 k1 l1][-1 0 0.731 /0 -1 0.964/0
0 1]. The twin law generated from |Fo| - |Fc| table was used to generate HKLF5 format file (Bolte, 2004) which is suitable
for a twin refinement by SHELXL-97 (Sheldrick, 2008). The refinement converged to the R-factor of 0.0474 for
Fo>4σ(Fo). All the spurious difference peaks have vanished. The refined domain fractions converged to the values
0.883 (2) and 0.117 (3). As the second component of the twin was weak it was not observed during the cell indexing.
All the hydrogens were discernible in the difference electron density map. Nevertheless all the aryl hydrogens were
fully constrained. The values of the used constraints were following: CarylH = 0.93 Å. UisoH=1.2UeqCaryl. The positional
parameters of the water hydrogens were restrained with O-H = 0.82 (1)Å, while Uiso(Hwater-oxygen)=1.5Ueq(Owater_oxygen).
Figure 1
View of the title molecule with the atom labelling scheme. The displacement ellipsoids are drawn at the 30% probability
level while the H atoms are shown as small spheres of arbitrary radii. The atoms labelled by "a" are related by the
symmetry operation -x, -y, -z.
Acta Cryst. (2013). E69, m508–m509
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Figure 2
The hydrogen bond motifs in the title structure. Black: C; blue: N; light blue: Co; green: Cl, red: O; grey (small): H.
Symmetry codes: (i): -x, 1 - y, -z, (iii): 1 - x, 1 - y, -z and (iv): 1 - x, -y, -z.
Diaquadichloridobis(pyridine-κN)cobalt(II)
Crystal data
[CoCl2(C5H5N)2(H2O)2]
Mr = 324.06
Triclinic, P1
Hall symbol: -P 1
a = 6.2028 (2) Å
b = 6.5971 (1) Å
c = 8.5963 (2) Å
α = 109.734 (2)°
β = 102.621 (3)°
γ = 97.031 (2)°
V = 315.65 (1) Å3
Z=1
F(000) = 165
Dx = 1.705 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2211 reflections
θ = 2.6–26.7°
µ = 1.77 mm−1
T = 293 K
Block, pink
0.25 × 0.2 × 0.18 mm
Data collection
Oxford Diffraction Xcalibur
diffractometer
Radiation source: Fine-focus sealed tube,
Enhance (Mo) X-ray Source
Graphite monochromator
ω scans
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin = 0.576, Tmax = 0.618
Acta Cryst. (2013). E69, m508–m509
2211 measured reflections
2211 independent reflections
1926 reflections with I > 2σ(I)
Rint = 0.000
θmax = 26.7°, θmin = 2.6°
h = −7→7
k = −8→8
l = −10→10
sup-3
supporting information
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.149
S = 1.16
2211 reflections
88 parameters
3 restraints
22 constraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: difference Fourier map
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0878P)2 + 0.6139P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.71 e Å−3
Δρmin = −0.99 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
C1
H1
C2
H2
C3
H3
C4
H4
C5
H5
N1
O1
H1A
H1B
Cl1
Co1
x
y
z
Uiso*/Ueq
0.2308 (7)
0.3593
0.2576 (7)
0.4012
0.0695 (8)
0.0834
−0.1391 (7)
−0.2690
−0.1549 (7)
−0.2975
0.0267 (5)
0.2699 (4)
0.264 (8)
0.365 (6)
−0.27270 (14)
0.0000
0.2281 (6)
0.2270
0.3179 (7)
0.3792
0.3160 (7)
0.3749
0.2252 (7)
0.2200
0.1418 (7)
0.0832
0.1418 (5)
0.2637 (4)
0.388 (4)
0.210 (6)
0.23327 (14)
0.0000
0.3845 (5)
0.3453
0.5588 (5)
0.6352
0.6187 (5)
0.7361
0.5014 (5)
0.5386
0.3281 (5)
0.2499
0.2680 (4)
0.0415 (4)
0.045 (6)
0.000 (6)
−0.06014 (12)
0.0000
0.0301 (9)
0.036*
0.0374 (10)
0.045*
0.0380 (10)
0.046*
0.0339 (9)
0.041*
0.0297 (8)
0.036*
0.0247 (7)
0.0299 (7)
0.045*
0.045*
0.0295 (3)
0.0209 (2)
Atomic displacement parameters (Å2)
C1
C2
C3
C4
C5
U11
U22
U33
U12
U13
U23
0.028 (2)
0.040 (2)
0.063 (3)
0.046 (3)
0.029 (2)
0.028 (2)
0.029 (2)
0.026 (2)
0.030 (2)
0.027 (2)
0.029 (2)
0.031 (2)
0.025 (2)
0.034 (2)
0.030 (2)
0.0014 (16)
0.0004 (18)
0.013 (2)
0.0138 (18)
0.0039 (16)
0.0024 (16)
−0.0014 (19)
0.014 (2)
0.0216 (19)
0.0112 (16)
0.0087 (17)
0.0059 (18)
0.0074 (18)
0.0147 (19)
0.0053 (17)
Acta Cryst. (2013). E69, m508–m509
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supporting information
N1
O1
Cl1
Co1
0.0250 (16)
0.0244 (15)
0.0237 (5)
0.0170 (3)
0.0209 (15)
0.0231 (14)
0.0240 (5)
0.0183 (4)
0.0256 (16)
0.0428 (17)
0.0383 (6)
0.0228 (4)
0.0024 (12)
0.0016 (11)
0.0052 (4)
−0.0001 (2)
0.0082 (13)
0.0134 (13)
0.0082 (4)
0.0053 (3)
0.0057 (13)
0.0117 (14)
0.0089 (4)
0.0035 (3)
Geometric parameters (Å, º)
C1—N1
C1—C2
C1—H1
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—N1
1.347 (5)
1.376 (5)
0.9300
1.375 (6)
0.9300
1.372 (6)
0.9300
1.379 (6)
0.9300
1.338 (5)
C5—H5
N1—Co1
O1—Co1
O1—H1A
O1—H1B
Cl1—Co1
Co1—N1i
Co1—O1i
Co1—Cl1i
0.9300
2.133 (3)
2.136 (2)
0.817 (10)
0.812 (10)
2.5078 (9)
2.133 (3)
2.136 (2)
2.5078 (9)
N1—C1—C2
N1—C1—H1
C2—C1—H1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
N1—C5—C4
N1—C5—H5
C4—C5—H5
C5—N1—C1
C5—N1—Co1
C1—N1—Co1
122.9 (4)
118.6
118.6
119.2 (4)
120.4
120.4
118.5 (4)
120.8
120.8
119.5 (4)
120.2
120.2
122.6 (4)
118.7
118.7
117.3 (3)
122.1 (3)
120.5 (3)
Co1—O1—H1A
Co1—O1—H1B
H1A—O1—H1B
N1—Co1—N1i
N1—Co1—O1i
N1i—Co1—O1i
N1—Co1—O1
N1i—Co1—O1
O1i—Co1—O1
N1—Co1—Cl1i
N1i—Co1—Cl1i
O1i—Co1—Cl1i
O1—Co1—Cl1i
N1—Co1—Cl1
N1i—Co1—Cl1
O1i—Co1—Cl1
O1—Co1—Cl1
Cl1i—Co1—Cl1
129 (3)
108 (3)
115 (3)
180.0
92.24 (11)
87.76 (11)
87.76 (11)
92.24 (11)
180.0
89.65 (8)
90.35 (8)
88.46 (7)
91.54 (7)
90.35 (8)
89.65 (8)
91.54 (7)
88.46 (7)
180.0
N1—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—N1
C4—C5—N1—C1
C4—C5—N1—Co1
C2—C1—N1—C5
C2—C1—N1—Co1
1.5 (6)
−0.4 (6)
−0.9 (6)
1.2 (6)
−0.1 (6)
177.4 (3)
−1.3 (6)
−178.8 (3)
C5—N1—Co1—O1i
C1—N1—Co1—O1i
C5—N1—Co1—O1
C1—N1—Co1—O1
C5—N1—Co1—Cl1i
C1—N1—Co1—Cl1i
C5—N1—Co1—Cl1
C1—N1—Co1—Cl1
−37.2 (3)
140.2 (3)
142.8 (3)
−39.8 (3)
−125.6 (3)
51.8 (3)
54.4 (3)
−128.2 (3)
Symmetry code: (i) −x, −y, −z.
Acta Cryst. (2013). E69, m508–m509
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supporting information
Hydrogen-bond geometry (Å, º)
D—H···A
ii
O1—H1A···Cl1
O1—H1B···Cl1iii
D—H
H···A
D···A
D—H···A
0.82 (3)
0.81 (4)
2.45 (3)
2.41 (4)
3.266 (3)
3.156 (3)
176 (5)
153 (4)
Symmetry codes: (ii) −x, −y+1, −z; (iii) x+1, y, z.
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